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Resolution and Determination of the Absolute Configuration of the Enantiomers of a trans ‐α‐Disulfoxide
Author(s) -
Allenmark Stig,
Grainger Richard S.,
Olsson Susanne,
Patel Bhaven
Publication year - 2011
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201100419
Subject(s) - chemistry , racemization , enantiomer , absolute configuration , homolysis , bond cleavage , resolution (logic) , stereochemistry , analytical chemistry (journal) , organic chemistry , radical , catalysis , artificial intelligence , computer science
The trans isomer of 2,7‐di‐ tert ‐butylnaphtho[1,8‐ cd ][1,2]dithiole 1,2‐dioxide, a vic ‐disulfoxide of the highest thermal stability reported to date, has been resolved into its enantiomers by preparative chiral liquid chromatography. This represents the first resolution achieved of a vic ‐disulfoxide. The absolute configuration of the isolated enantiomers has been determined to be (+)‐( S , S ), (–)‐( R , R ) from a comparison of experimental and calculated ECD and VCD spectra. The long‐wavelength ECD band at about 330 nm had a positive sign in the (+)‐( S , S )‐form and a negative sign in the (–)‐( R , R )‐enantiomer. A photocatalyzed slow decrease in optical activity was observed in solution, most likely due to racemization by homolytic (O)S–S(O) bond cleavage and bissulfinyl radical recombination.